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Diffusion: the movement of particles in a solid from an area of high concentration to an area of low concentration, resulting in the uniform distribution of the substance Diffusion is process which is NOT due to the action of a force, but a result of the random movements of atoms (statistical problem) 1. Diffusivity and 2 Ficks laws 2. Atomistic mechanisms of diffusion 3. Temperature dependence and Arrenius plot 4. Industrial applications - carburized steel, - dopants in silicon
Chapter 5
J = D
dC dx
J flux of atoms, atoms/(m2 s): the number of particles which pass through a unit area in a unit of time;
m 2 dC atoms 1 atoms J 2 = D s dx m3 m m s
- sign: flux direction is from the higher to the lower concentration; i.e. it is the opposite to the concentration gradient
Diffusivity D depends on: 1. Diffusion mechanism 2. Temperature of diffusion 3. Type of crystal structure (bcc > fcc) 4. Crystal imperfections 5. Concentration of diffusing species
Chapter 5
Non-Steady-State Diffusion
In practice the concentration of solute atoms at any point in the material changes with time non-steady-state diffusion
dC x d dC x = D dt dx dx
2C dC x =D 2 x dt
Change in concentration in 2 semi-infinite rods of Cu and Ni caused by diffusion, From G. Gottstein Physical Foundations of Material Science
If D D(x), in 1D case:
The rate of compositional change is equal to the diffusivity times the rate of the change of the concentration gradient
In 3D case:
2C 2 C 2 C dC x = D x 2 + y 2 + z 2 dt
Chapter 5
dt
c( x, t ) c1 =
c2 c1
x 2 Dt
e d =
2
c2 c1 x 1 + erf 2 2 Dt
where erf ( z ) =
x z= 2 Dt
e
0
Chapter 5
Solid B
Cs C x x = erf C S Co 2 Dt
Chapter 5
Error function
z=
x 2 Dt
Chapter 5
Q: Consider the gas carburizing of a gear of 1018 steel (C 0.18 wt %) at 927C. Calculate the time
necessary to increase the C content to 0.35 wt % at 0.40 mm below the surface of the gear. Assume the C content at the surface to be 1.15 wt % and that the nominal C content of the steel gear before carburizing is 0.18 wt %. D (C in iron) at 927C = 1.28 10-11 m2/s
Chapter 5
Chapter 5
Vacancies
The simplest point defect is the vacancy (V) an atom site from which an atom is missing Vacancies are always present; their number NV depends on temperature (T)
NV = N e
EV kT
T absolute temperature
vacancy
Chapter 5
higher Tmelt stronger bonding between atoms high activation energy to move V
Chapter 5
Kirkendall effect
Marker at the diffusion interface move slightly in the opposite direction to the most rapidly moving species vacancies can move!
Chapter 5
Total 8 eV 2 eV 4 eV 3.6 eV
Chapter 5
Anisotropy Effects
Chapter 5
Carbon diffusion in Fe
Jump frequency [s-1] of an atom is given by:
= e
Gm kT
There is a fundamental relationship between the jump frequency and the diffusion coefficient D which is independent of mechanism and crystal structure:
D=
2
6
2 6
J = JMN - JNM
the jump distance of the diffusing atom =1/ the time interval between two jumps
1 2 1 2 A A J = CM CN 4 3 4 3
D= a 2 24
Chapter 5
Carbon diffusion in Fe
Can be derived from an atomistic considerations of the diffusion processes C atoms are located on the octahedral interstitial sites (black circles)
J = JMN - JNM
Only of possible jumps of C atoms lead to flux in +x Only 2/3 of all C atoms can jump in x direction
D=
2
6
2 6
D=
a 2 24
Chapter 5
D = Do e
EA RT
D diffusivity, m2/s D0- proportionality constant, m2/s, independent of T EA activation energy for diffusing species, J/mol
R molar gas constant
R = 8.314 J mol-1 K-1; or 1.987cal mol-1K-1
T absolute temperature
Chapter 5
Activation energy
A+BC+D A (initial state) A* (final state)
only a fraction of the molecules or atoms in a system will have sufficient energy to reach E* A thermally active process is one which requires a definite amount of thermal energy to overcome an activation energy barrier and enter the reactive state
Chapter 5
Bolzmanns equation
On the basis of statistical analysis, Bolzmanns results showed that the probability of finding a molecule or atom at an energy level E* > the average energy E of all the molecules or atoms in a system at a particular temperature T, K, was:
Probability e
E* E kT
The fraction of atoms or molecules in a system having energies > E* at a given T (where E* is much greater than the average energy of any atom or molecule:
n N total = Ce
E* kT
Chapter 5
Rate _ of _ reaction = C e
C rate constant, independent of T EA activation energy R molar gas constant
R = 8.314 J mol-1 K-1; or 1.987cal mol-1K-1
T absolute temperature
Chapter 5
10
ln rate = ln C
ln rate = a
EA RT
ln C = b 1 x= T
y = b + m x
EA 2.303RT
Chapter 5
Q.: The diffusivity of Ag atoms in solid silver metal is 1.0X1017 m2/s at 500oC and 7.0x10-13 m2/s at 1000oC. Calculate the activation energy (J/mole) for the diffusion of Ag in Ag in the T range 500 to 1000oC.
Chapter 5
11
Chapter 5
Dopants activation
Dopants can be incorporated into Si wafer to change their electrical conducting characteristics
12
Q: If boron, B, is diffused into a thick slice of Si with no previous B in it at a temperature of 1100C for 5 h, what is the depth below the surface at which the concentration is 1017 atoms/cm3 if the surface concentration is 1018 atoms/cm3? D = 4 10-13 cm2/s for B diffusing in Si at 1100C.
Chapter 5
Summary
Diffusion: the movement of particles in a solid from an area of high concentration to an area of low concentration, resulting in the uniform distribution of the substance Ficks first diffusion law: for steady-state diffusion condition (no change in the system with time), the net flow of atoms is equal to the diffusivity D times the diffusion gradient dC/dx
J = D
dC dx
Ficks second diffusion law: The rate of compositional change is equal to the diffusivity times the rate of the change of the concentration gradient
2C dC x =D 2 dt x
Diffusion rate in a system will increase with temperature:
EA RT
D = Do e
Chapter 5
13